Chiral Organic Ion Pair Catalysts Assembled Through a Hydrogen- Bonding Network

Transcription

1 Supporting nline Material for Chiral rganic Ion Pair Catalysts Assembled Through a Hydrogen- Bonding etwork Daisuke Uraguchi, Yusuke Ueki, Takashi oi* *To whom correspondence should be addressed. tooi@apchem.nagoya-u.ac.jp This PDF file includes: Published 27 August 2009 on Science Express DI: /science Materials and thods Figs. S1 to S3 Tables. S1 to S3 References

2 Supporting nline Material for Chiral rganic Ion Pair Catalysts Assembled through a Hydrogen-Bonding etwork Daisuke Uraguchi, Yusuke Ueki, Takashi oi Department of Applied Chemistry, Graduate School of Engineering, agoya University, agoya , Japan tooi@apchem.nagoya-u.ac.jp General Information: Infrared spectra were recorded on a JASC FT/IR-300E spectrometer. 1 H MR spectra were recorded on a Varian IVA-500 (500 MHz) or IVA-700 (700 MHz) spectrometer. Chemical shifts are reported in ppm from the solvent resonance (CD 3 D; 3.31 ppm) or tetramethylsilane (0.0 ppm) resonance as the internal standard (CDCl 3 ). Data are reported as follows: chemical shift, integration, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, sex = sextet, sept = septet, oct = octet, m = multiplet, and br = broad) and coupling constants (Hz). 13 C MR spectra were recorded on a Varian IVA-500 (126 MHz) or IVA-700 (175 MHz) spectrometer with complete proton decoupling. Chemical shifts are reported in ppm from the solvent resonance as the internal standard (CDCl 3 ; ppm, CD 3 D; 49.0 ppm). 31 P MR spectra were recorded on a Varian rcury-300bb (121 MHz) spectrometer with complete proton decoupling. Chemical shifts are reported in ppm from H 3 P 4 (0.0 ppm) resonance as the external standard. ptical rotations were measured on a JASC DIP-1000 polarimeter. The high resolution mass spectra were measured on an BRUKER DALTICS microtf focus-kr spectrometer. Analytical thin layer chromatography (TLC) was performed on rck precoated TLC plates (silica gel 60 GF 254, 0.25 mm). Flash column chromatography was performed on silica gel 60 (spherical, μm; Kanto Chemical Co., Inc.). Enantiomeric excesses were determined by HPLC analysis using chiral columns (φ 4.6 mm x 250 mm, DAICEL CHIRALCEL D-H (DH), CHIRALPAK IA (IA) or CHIRALPAK IC (IC)) with hexane (H), isopropyl alcohol (IPA), and ethanol (EtH) as eluent. Toluene and tetrahydrofuran (THF) were supplied from Kanto Chemical Co., Inc. as Dehydrated solvent system. Tetraaminophosphonium salts 1a Cl and 1b Cl (S1-3), azlactone 2 (S4), and α,β-unsaturated -acylbenzotriazoles 3a-k (S5) were prepared by following the literature procedures. ther simple chemicals were purchased and used as such. Experimental Section: Characterization of Tetraaminophosphonium Salts 1: 1b Cl: 1 H MR (500 MHz, CDCl 3 ) δ 7.70 (2H, d, J = 16.5 Hz), 7.68 (4H, br), 7.59 (4H, dd, J = 7.5, 1.0 Hz), 7.39 (4H, t, J = 7.5 Hz), 7.32 (4H, brt, J = 7.5 Hz), 7.28 (2H, t, J = 7.5 Hz), 7.20 (2H, t, J = 7.5 Hz), 3.79 (2H, dd, J P-H = 21.0 Hz, J H-H = 5.0 Hz), (2H, m), (2H, m), 1.80 (6H, d, J P-H = 10.0 Hz), (2H, m), 0.84 (6H, t, J = 7.0 Hz), 0.56 (6H, d, J = 7.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 148.0, (d, J P-C = 11.4 Hz), 128.7, 128.6, 128.0, 127.7, 127.6, 127.0, 73.4 (d, J P-C = 12.6 Hz), 70.9 (d, J P-C = 9.3 Hz), 36.1, 32.2 (d, J P-C = 6.0 Hz), 25.2, 18.9, 12.1; 31 P MR (121 MHz, CDCl 3 ) δ 37.7; IR (KBr): 3059, 2967, 2874, 1495, 1446, 1358, 1334, 1191, 1035, 751 cm -1 ; HRMS (ESI-TF) Calcd for C 38 H 48 4 P + ([M-Cl] + ) Found ; [α] D (c = 0.95, CHCl 3 ). Counter Anion Exchange Procedure to Prepare Chiral Tetraaminophosphonium Phenoxide 1 (Ar) 3 H 2 (S6): Chiral tetraaminophosphonium chloride 1 Cl was transformed into the corresponding phosphonium hydroxide 1 H by passing a methanolic solution of 1 Cl through an ion-exchange resin (amberlyst A-26, H - form). The resulting 1 H was then treated with phenol (3.0 equiv) in methanol at room temperature. The resulting mixture was co-evaporated with benzene - S1 -

3 three times, and subsequent crystallization of the residue from hexane and diethyl ether afforded white solids, which were collected by filtration and dried under reduced pressure to give the title compound. 1a (Ph) 3 H 2 : 1 H MR (700 MHz, CD 3 D) δ 7.62 (4H, d, J = 7.0 Hz), 7.45 (4H, t, J = 7.0 Hz), 7.34 (2H, t, J = 7.7 Hz), 7.33 (4H, br), 7.32 (4H, t, J = 7.7 Hz), 7.28 (2H, t, J = 7.7 Hz), 7.09 (6H, t, J = 7.0 Hz), 6.71 (6H, d, J = 7.0 Hz), 6.66 (3H, t, J = 7.0 Hz), 4.00 (2H, dd, J P-H = 19.6 Hz, J H-H = 6.3 Hz), 1.89 (6H, d, J P-H = 9.8 Hz), 1.87 (2H, oct, J = 6.3 Hz), 0.95 (6H, d, J = 6.3 Hz), 0.49 (6H, d, J = 6.3 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 161.6, 148.9, (d, J P-C = 12.8 Hz), 130.2, 130.0, 129.2, 129.0, 128.9, 128.7, 127.9, 118.6, 117.4, 72.5 (d, J P-C = 10.7 Hz), 71.6 (d, J P-C = 10.7 Hz), 32.8 (d, J P-C = 6.1 Hz), 30.9, 22.7, 19.8; 31 P MR (121 MHz, CD 3 D) δ a (4- C 6 H 4 ) 3 H 2 : 1 H MR (700 MHz, CD 3 D) δ 7.62 (4H, d, J = 7.7 Hz), 7.45 (4H, t, J = 7.7 Hz), 7.35 (2H, t, J = 7.7 Hz), 7.33 (4H, br), 7.32 (4H, t, J = 7.7 Hz), 7.28 (2H, t, J = 7.7 Hz), 6.90 (6H, d, J = 8.4 Hz), 6.61 (6H, d, J = 8.4 Hz), 4.01 (2H, dd, J P-H = 19.6 Hz, J H-H = 6.3 Hz), 2.19 (9H, s), 1.89 (6H, d, J P-H = 9.8 Hz), 1.87 (2H, oct, J = 6.3 Hz), 0.95 (6H, d, J = 6.3 Hz), 0.49 (6H, d, J = 6.3 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 159.0, 148.9, (d, J P-C = 13.3 Hz), 130.6, 130.0, 129.2, 129.0, 128.9, 128.7, 127.9, 127.6, 117.1, 72.5 (d, J P-C = 10.6 Hz), 71.7 (d, J P-C = 10.0 Hz), 32.8 (d, J P-C = 6.1 Hz), 30.9, 22.7, 20.5, 19.8; 31 P MR (121 MHz, CD 3 D) δ a (4-Cl C 6 H 4 ) 3 H 2 : 1 H MR (700 MHz, CD 3 D) δ 7.62 (4H, d, J = 7.7 Hz), 7.44 (4H, t, J = 7.7 Hz), 7.34 (2H, t, J = 7.7 Hz), 7.33 (4H, br), 7.32 (4H, t, J = 7.7 Hz), 7.28 (2H, t, J = 7.7 Hz), 7.07 (6H, d, J = 8.4 Hz), 6.68 (6H, d, J = 8.4 Hz), 4.00 (2H, dd, J P-H = 19.6 Hz, J H-H = 6.3 Hz), 1.89 (6H, d, J P-H = 9.8 Hz), 1.86 (2H, oct, J = 6.3 Hz), 0.95 (6H, d, J = 6.3 Hz), 0.49 (6H, d, J = 6.3 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 160.0, 148.9, (d, J P-C = 12.6 Hz), 130.0, 129.2, 129.0, 128.9, 128.7, 127.9, 123.4, 118.6, 72.5 (d, J P-C = 11.4 Hz), 71.6 (d, J P-C = 10.0 Hz), 32.8 (d, J P-C = 6.1 Hz), 30.9, 22.7, 19.8, one carbon was not found probably due to overlapping; 31 P MR (121 MHz, CD 3 D) δ a (2-Cl C 6 H 4 ) 3 H 2 : 1 H MR (700 MHz, CD 3 D) δ 7.62 (4H, d, J = 7.7 Hz), 7.45 (4H, t, J = 7.7 Hz), 7.34 (2H, t, J = 7.7 Hz), 7.33 (4H, br), 7.32 (4H, t, J = 7.7 Hz), 7.28 (2H, t, J = 7.7 Hz), 7.17 (3H, dd, J = 7.7, 1.4 Hz), 6.98 (3H, td, J = 7.7, 1.4 Hz), 6.80 (3H, dd, J = 7.7, 1.4 Hz), 6.54 (3H, td, J = 7.7, 1.4 Hz), 4.00 (2H, dd, J P-H = 19.6 Hz, J H-H = 6.3 Hz), 1.89 (6H, d, J P-H = 10.5 Hz), 1.87 (2H, oct, J = 6.3 Hz), 0.95 (6H, d, J = 6.3 Hz), 0.49 (6H, d, J = 6.3 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 159.1, 148.9, (d, J P-C = 12.8 Hz), 130.5, 130.0, 129.2, 129.0, 128.9, 128.7, 128.6, 127.9, 123.1, 119.4, 118.1, 72.5 (d, J P-C = 10.7 Hz), 71.7 (d, J P-C = 10.0 Hz), 32.8 (d, J P-C = 6.0 Hz), 30.9, 22.7, 19.8; 31 P MR (121 MHz, CD 3 D) δ a (3-Cl C 6 H 4 ) 3 H 2 : 1 H MR (500 MHz, CD 3 D) δ 7.62 (4H, d, J = 7.5 Hz), 7.45 (4H, t, J = 7.5 Hz), 7.35 (2H, t, J = 7.5 Hz), 7.34 (4H, br), 7.32 (4H, t, J = 7.5 Hz), (2H, m), 7.05 (3H, t, J = 8.0 Hz), 6.71 (3H, t, J = 2.0 Hz), 6.65 (3H, d, J = 8.0 Hz), 6.62 (3H, d, J = 8.0 Hz), 4.01 (2H, dd, J P-H = 20.0 Hz, J H-H = 6.5 Hz), 1.89 (6H, d, J P-H = 10.0 Hz), 1.87 (2H, oct, J = 6.5 Hz), 0.95 (6H, d, J = 6.5 Hz), 0.49 (6H, d, J = 6.5 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 163.1, 148.9, (d, J P-C = 13.4 Hz), 135.5, 131.1, 130.0, 129.2, 129.0, 128.9, 128.7, 127.9, 118.4, 117.7, 116.1, 72.5 (d, J P-C = 10.7 Hz), 71.6 (d, J P-C = 10.2 Hz), 32.8 (d, J P-C = 6.1 Hz), 30.9, 22.7, 19.8; 31 P MR (121 MHz, CD 3 D) δ a (3,5-Cl 2 C 6 H 3 ) 3 H 2 : 1 H MR (500 MHz, CD 3 D) δ 7.62 (4H, d, J = 7.5 Hz), 7.45 (4H, t, J = 7.5 Hz), 7.35 (2H, t, J = 7.5 Hz), 7.34 (4H, br), 7.32 (4H, t, J = 7.5 Hz), (2H, m), 6.68 (3H, t, J = 2.0 Hz), 6.64 (6H, d, J = 2.0 Hz), 4.01 (2H, dd, J P-H = 20.0 Hz, J H-H = 6.5 Hz), 1.89 (6H, d, J P-H = 10.0 Hz), 1.87 (2H, oct, J = 6.5 Hz), 0.95 (6H, d, J = 6.5 Hz), 0.49 (6H, d, J = 6.5 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 164.0, 148.9, (d, J P-C = 12.8 Hz), 136.1, 130.0, 129.2, 129.0, 128.9, 128.7, 127.9, 118.1, 116.5, 72.5 (d, J P-C = 10.7 Hz), 71.7 (d, J P-C = 10.0 Hz), 32.8 (d, J P-C = 6.0 Hz), 30.9, 22.7, 19.8; 31 P MR (121 MHz, CD 3 D) δ 36.4; IR (KBr): 2964, 1578, 1446, 1423, 1370, 1269, 1019, 936, 797, 753 cm S2 -

4 1b (3,5-Cl 2 C 6 H 3 ) 3 H 2 : 1 H MR (500 MHz, CD 3 D) δ 7.61 (4H, d, J = 7.5 Hz), 7.45 (4H, t, J = 7.5 Hz), 7.35 (2H, t, J = 7.5 Hz), 7.34 (4H, br), 7.33 (4H, t, J = 7.5 Hz), (2H, m), 6.68 (3H, t, J = 2.0 Hz), 6.64 (6H, d, J = 2.0 Hz), 4.09 (2H, dd, J P-H = 19.0 Hz, J H-H = 4.0 Hz), 1.89 (6H, d, J P-H = 10.0 Hz), 1.78 (2H, dqd, J = 13.0, 7.0, 2.5 Hz), 1.42 (2H, qtd, J = 7.0, 4.0, 2.5 Hz), 0.93 (2H, dqd, J = 13.0, 7.0, 4.0 Hz), 0.76 (6H, t, J = 7.0 Hz), 0.62 (6H, d, J = 7.0 Hz), -H and -H protons were not found due to deuteration; 13 C MR (175 MHz, CD 3 D) δ 163.9, 148.9, (d, J P-C = 12.6 Hz), 136.0, 130.0, 129.1, 129.0, 128.8, 128.7, 127.9, 118.1, 116.5, 72.8 (d, J P-C = 10.7 Hz), 71.5 (d, J P-C = 10.7 Hz), 37.7, 32.6 (d, J P-C = 6.0 Hz), 26.0, 18.8, 12.2; 31 P MR (121 MHz, CD 3 D) δ 36.8; IR (KBr): 2971, 1581, 1424, 1374, 1210, 1034, 936, 827, 796, 752 cm -1. Characterization of α,β-unsaturated -Acylbenzotriazoles 3: 3a (S5): 1 H MR (500 MHz, CDCl 3 ) δ 8.43 (1H, d, J = 7.5 Hz), 8.17 (1H, d, J = 16.0 Hz), 8.16 (1H, d, J = 7.5 Hz), 8.14 (1H, d, J = 16.0 Hz), (2H, m), 7.70 (1H, t, J = 7.5 Hz), 7.54 (1H, t, J = 7.5 Hz), (3H, m). 3b (S7): 1 H MR (500 MHz, CDCl 3 ) δ 8.43 (1H, dt, J = 8.0, 1.0 Hz), 8.15 (1H, dt, J = 8.0, 1.0 Hz), 8.12 (1H, d, J = 15.0 Hz), 8.00 (1H, d, J = 15.0 Hz), 7.73 (2H, d, J = 9.0 Hz), 7.68 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.53 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 6.99 (2H, d, J = 9.0 Hz), 3.89 (3H, s). 3c: 1 H MR (700 MHz, CDCl 3 ) δ 8.40 (1H, dt, J = 8.4, 1.4 Hz), 8.15 (1H, dt, J = 8.4, 1.4 Hz), 8.11 (1H, d, J = 15.4 Hz), 8.06 (1H, d, J = 15.4 Hz), 7.68 (1H, ddd, J = 8.4, 7.0, 1.4 Hz), (4H, m), 7.53 (1H, ddd, J = 8.4, 7.0, 1.4 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 163.8, Br 147.4, 146.5, 133.1, 132.6, 131.5, 130.5, 130.4, 126.5, 126.1, 120.4, 116.8, 114.9; IR (KBr): 1699, 1618, 1486, 1450, 1405, 1389, 1072, 995, 790, 753 cm -1 ; HRMS (ESI-TF) Calcd for C 15 H 11 Br 3 a + ([M+a] + ) , Found , d (S7): 1 H MR (500 MHz, CDCl 3 ) δ 8.48 (1H, d, J = 15.5 Hz), 8.42 (1H, d, J = 8.0 Hz), 8.16 (1H, d, J = 8.0 Hz), 8.07 (1H, d, J = 15.5 Hz), 7.86 (1H, d, J = 7.5 Hz), 7.69 (1H, t, J = 8.0 Hz), 7.54 (1H, d, J = 8.0 Hz), 7.37 (1H, t, J = 7.5 Hz), 7.31 (1H, t, J = 7.5 Hz), 7.28 (1H, d, J = 7.5 Hz), 2.56 (3H, s). 3e: 1 H MR (500 MHz, CDCl 3 ) δ 8.41 (1H, d, J = 8.0 Hz), 8.17 (1H, d, J = 8.0 Hz), 8.13 (1H, d, J = 16.0 Hz), 8.06 (1H, d, J = 16.0 Hz), 7.90 (1H, t, J = 1.0 Hz), 7.70 (1H, t, J = 8.0 Hz), 7.67 (1H, dd, J = 8.0, 1.0 Hz), 7.60 (1H, dd, J = 8.0, 1.0 Hz), 7.55 (1H, t, J = 8.0 Hz), 7.35 (1H, t, J = 8.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 163.6, 146.9, 146.5, 136.3, 134.3, 131.7, 131.5, 130.7, 130.6, Br 127.6, 126.5, 123.4, 120.4, 117.6, 114.9; IR (KBr): 1704, 1628, 1452, 1372, 1175, 1074, 998, 984, 758 cm -1 ; HRMS (ESI-TF) Calcd for C 15 H 11 Br 3 + ([M+H] + ) , Found , f: 1 H MR (500 MHz, CDCl 3 ) δ 9.04 (1H, d, J = 15.5 Hz), 8.46 (1H, dt, J = 8.0, 1.0 Hz), 8.34 (1H, d, J = 8.0 Hz), 8.25 (1H, d, J = 15.5 Hz), 8.17 (1H, dt, J = 8.0, 1.0 Hz), 8.09 (1H, d, J = 8.0 Hz), 8.00 (1H, d, J = 8.0 Hz), 7.93 (1H, d, J = 8.0 Hz), 7.71 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.65 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), (1H, t, J = 8.0 Hz), (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.55 (1H, ddd, J = 8.0, 7.0, 1.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 164.0, 146.5, 145.5, 133.9, 132.0, 131.8, 131.6, 131.3, 130.5, 129.1, 127.5, 126.6, 126.4, 126.2, 125.7, 123.3, 120.3, 118.3, 115.0; IR (KBr): 1700, 1605, 1572, 1449, 1376, 1352, 1169, 982, 768, 746 cm -1 ; HRMS (ESI-TF) Calcd for C 19 H ([M+H] + ) Found g (S8): 1 H MR (500 MHz, CDCl 3 ) δ 8.41 (1H, dd, J = 8.0, 1.0 Hz), 8.15 (1H, dd, J = 8.0, 1.0 Hz), 7.98 (1H, d, J = 16.0 Hz), 7.88 (1H, d, J = 16.0 Hz), 7.68 (1H, t, J = 8.0 Hz), 7.62 (1H, d, J = 2.0 Hz), 7.53 (1H, t, J = 8.0 Hz), 6.87 (1H, d, J = 3.5 Hz), 6.57 (1H, dd, J = 3.5, 2.0 Hz). - S3 -

5 3h (S5): 1 H MR (500 MHz, CDCl 3 ) δ 8.36 (1H, d, J = 8.0 Hz), 8.13 (1H, d, J = 8.0 Hz), 7.66 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), (3H, m), 2.13 (3H, d, J = 5.5 Hz). 3i: 1 H MR (500 MHz, CDCl 3 ) δ 8.37 (1H, dt, J = 8.0, 1.0 Hz), 8.14 (1H, dt, J = 8.0, 1.0 Hz), 7.66 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.53 (1H, d, J = 15.0 Hz), 7.52 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), (2H, dtd, J = 7.5, 5.0, 2.5 Hz), 1.61 (2H, quin-t, J = 7.5, 2.5 Hz), (4H, m), 0.93 (3H, t, J = 7.5 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 163.9, 155.2, 146.4, 131.6, 130.3, 126.3, 120.3, 119.9, 114.9, 33.2, 31.5, 27.7, 22.6, 14.1; IR (KBr): 2956, 2929, 1716, 1637, 1485, 1450, 1377, 1286, 988, 751 cm -1 ; HRMS (ESI-TF) Calcd for C 14 H ([M+H] + ) Found j: 1 H MR (500 MHz, CDCl 3 ) δ 8.35 (1H, dd, J = 8.0, 1.0 Hz), 8.13 (1H, dd, J = 8.0, 1.0 Hz), 7.66 (1H, td, J = 8.0, 1.0 Hz), 7.56 (1H, d, J = 16.0 Hz), 7.52 (1H, td, J = 8.0, 1.0 Hz), 7.51 (1H, dt, J = 16.0, 5.0 Hz), 7.32 (2H, t, J = 7.5 Hz), 7.24 (2H, d, J = 7.5 Hz), 7.23 (1H, t, J = 7.5 Hz), 2.93 (2H, t, J = 8.0 Hz), 2.77 (2H, td, J = 8.0, 5.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 163.6, 153.4, 146.3, 140.5, 131.5, 130.3, 128.7, 128.4, 126.4, 126.2, 120.5, 120.2, 114.8, 34.7, 34.3; IR (KBr): 3029, 2904, 1711, 1632, 1450, 1380, 1077, 995, 957, 819, 754, 716 cm -1 ; HRMS (ESI-TF) Calcd for C 17 H ([M+H] + ) Found k: 1 H MR (500 MHz, CDCl 3 ) δ 8.36 (1H, dt, J = 8.5, 1.0 Hz), 8.13 (1H, dt, J = 8.5, 1.0 Hz), 7.66 (1H, ddd, J = 8.5, 7.0, 1.0 Hz), 7.51 (1H, ddd, J = 8.5, 7.0, 1.0 Hz), 7.47 (1H, dd, J = 19.0, 3.5 Hz), 7.44 (1H, d, J = 19.0 Hz), 2.39 (1H, tq, J = 12.5, 3.5 Hz), 1.92 (2H, brd, J = 12.5 Hz), 1.83 (2H, dquin, J = 12.5, 3.5 Hz), 1.73 (1H, dquin-t, J = 12.5, 3.5, 1.5 Hz), 1.37 (2H, qt, J = 12.5, 3.5 Hz), 1.32 (2H, q, J = 12.5 Hz), 1.27 (2H, qt, J = 12.5, 3.5 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 164.2, 159.7, 146.4, 131.6, 130.3, 126.2, 120.2, 117.7, 114.9, 41.4, 31.7, 26.0, 25.8; IR (KBr): 2926, 2852, 1715, 1634, 1449, 1378, 987, 959, 826, 750 cm -1 ; HRMS (ESI-TF) Calcd for C 15 H ([M+H] + ) Found Representative Procedure for Chiral Tetraaminophosphonium Phenoxide 1 (Ar) 3 H 2 -Catalyzed Asymmetric Conjugate Addition of Azlactone 2: α,β-unsaturated -acylbenzotriazole 3a (49.9 mg, 0.2 mmol) and 1b (3,5-Cl 2 C 6 H 3 ) 3 H 2 (0.01 equiv, 2.16 mg, 2.0 μmol) were placed in a dried test tube and dissolved into toluene (0.2 ml) under Ar atmosphere. Azlactone 2a (28.0 mg, 0.22 mmol) was then introduced dropwise slowly at 40 C and the stirring was continued for 4 hours. A solution of trifluoroacetic acid in toluene (0.5 M, 20 μl) was added to the reaction mixture. The mixture was poured into ice-cooled 1 HCl aqueous solution and the aqueous phase was extracted with ethyl acetate (EA). The combined organic phase was washed with brine, dried over a 2 S 4, and filtered. All volatiles were removed by evaporation and the diastereomeric ratio was determined by 1 H MR analysis of the crude aliquot. Purification of the residue by column chromatography on silica gel (H/EA = 5:1 as eluent) afforded 4a in 95% yield (71.5 mg, 0.19 mmol), Ph whose enantiomeric excess was determined to be 95% ee by HPLC analysis. 4a: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 24.5 min (minor diastereomer), 27.5 min (major; major diastereomer), 30.5 min (minor; major diastereomer), 38.0 min (minor diastereomer); 1 H MR (700 MHz, CDCl 3 ) δ 8.23 (1H, dt, J = 8.4, 0.7 Hz), 8.12 (1H, dt, J = 8.4, 0.7 Hz), 7.64 (1H, ddd, J = 8.4, 7.0, 0.7 Hz), 7.51 (1H, ddd, J = 8.4, 7.0, 0.7 Hz), (2H, m), (3H, m), 6.28 (1H, dd, J = 4.2, 2.1 Hz), 4.24 (1H, td, J = 7.0, 4.2 Hz), 4.18 (1H, dd, J = 17.5, 7.0 Hz), 4.09 (1H, dd, J = 17.5, 7.0 Hz), 2.79 (1H, sept-d, J = 7.0, 2.1 Hz), 1.18 (3H, d, J = 7.0 Hz), 1.04 (3H, d, J = 7.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 170.2, 169.9, 164.5, 146.3, 134.5, 131.1, 130.8, 129.7, 128.4, 128.2, 126.5, 120.4, 114.5, 44.1, 99.7, 36.1, 28.1, 18.9, one carbon was not found probably due to overlapping; IR (liq. film): 2973, 1781, 1737, 1451, 1390, 1167, 1064, 995, 965, 752 cm -1 ; HRMS (ESI-TF) Calcd for C 21 H a ([M+a] + ) Found S4 -

6 4b: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 33.6 min (minor diastereomer), 39.5 min (minor; major diastereomer), 41.8 min (major; major diastereomer), 53.9 min (minor diastereomer); 1 H MR (700 MHz, CDCl 3 ) δ 8.24 (1H, dt, J = 8.4, 0.7 Hz), 8.13 (1H, dt, J = 8.4, 0.7 Hz), 7.65 (1H, ddd, J = 8.4, 7.7, 0.7 Hz), 7.51 (1H, ddd, J = 8.4, 7.7, 0.7 Hz), 7.15 (2H, d, J = 8.4 Hz), 6.80 (2H, d, J = 8.4 Hz), 6.26 (1H, dd, J = 4.2, 2.1 Hz), 4.19 (1H, td, J = 7.7, 4.2 Hz), 4.16 (1H, dd, J = 17.5, 7.7 Hz), 4.04 (1H, dd, J = 17.5, 7.7 Hz), 3.75 (3H, s), 2.81 (1H, sept-d, J = 7.7, 2.1 Hz), 1.19 (3H, d, J = 7.7 Hz), 1.08 (3H, d, J = 7.7 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 170.2, 169.8, 164.6, 159.3, 146.3, 131.1, , , 126.5, 126.2, 120.4, 114.5, 113.8, 99.8, 55.3, 43.4, 36.3, 28.1, 19.0, one carbon was not found probably due to overlapping; IR (liq. film): 2972, 1779, 1738, 1515, 1451, 1389, 1254, 1065, 996, 966, 753 cm -1 ; HRMS (ESI-TF) Calcd for C 22 H a ([M+a] + ) Found Br 4c: IA, H/EtH = 2:1, flow rate = 0.5 ml/min, λ = 210 nm, 26.4 min (major; major diastereomer), 33.9 min (minor diastereomer), 45.4 min (minor diastereomer), 68.9 min (minor; major diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.22 (1H, dt, J = 8.0, 1.0 Hz), 8.13 (1H, dt, J = 8.0, 1.0 Hz), 7.66 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.53 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.42 (2H, dt, J = 8.5, 2.5 Hz), 7.14 (2H, dt, J = 8.5, 2.5 Hz), 6.25 (1H, dd, J = 4.0, 2.0 Hz), 4.20 (1H, ddd, J = 7.5, 6.0, 4.0 Hz), 4.16 (1H, dd, J = 17.0, 7.5 Hz), 4.05 (1H, dd, J = 17.0, 6.0 Hz), 2.83 (1H, sept-d, J = 7.0, 2.0 Hz), 1.20 (3H, d, J = 7.0 Hz), 1.08 (3H, d, J = 7.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 170.2, 169.9, 164.3, 146.4, 133.6, 131.6, 131.3, 131.1, 130.9, 126.6, 122.4, 120.5, 114.4, 99.4, 43.7, 36.0, 28.2, , ; IR (liq. film): 2973, 1782, 1738, 1487, 1450, 1389, 1167, 1065, 968, 753 cm -1 ; HRMS (ESI-TF) Calcd for C 21 H Bra ([M+a] + ) , Found , d: IA, H/IPA/EtH = 36:1:3, flow rate = 0.5 ml/min, λ = 210 nm, 26.3 min (major; major diastereomer), 32.3 min (minor diastereomer), 34.6 min (minor diastereomer), 38.4 min (minor; major diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.22 (1H, dd, J = 8.0, 1.0 Hz), 8.12 (1H, dd, J = 8.0, 1.0 Hz), 7.64 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.51 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), (4H, m), 6.25 (1H, dd, J = 5.0, 2.0 Hz), 4.52 (1H, ddd, J = 8.0, 7.0, 5.0 Hz), 4.20 (1H, dd, J = 18.0, 8.0 Hz), 4.06 (1H, dd, J = 18.0, 7.0 Hz), 2.85 (1H, sept-d, J = 7.0, 2.0 Hz), 1.22 (3H, d, J = 7.0 Hz), 1.13 (3H, d, J = 7.0 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 170.2, 169.7, 164.4, 146.2, 138.1, 133.3, 131.0, 130.9, 130.7, 128.3, 127.8, 126.4, 125.6, 120.3, 114.4, 100.4, 39.1, 36.9, 28.2, 20.2, , ; IR (liq. film): 2972, 1780, 1738, 1450, 1390, 1064, 968, 911, 752, 730 cm -1 ; HRMS (ESI-TF) Calcd for C 22 H a ([M+a] + ) Found Br 4e: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 24.5 min (minor diastereomer), 27.5 min (major; major diastereomer), 31.0 min (minor; major diastereomer), 36.5 min (minor diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.24 (1H, dt, J = 8.5, 1.0 Hz), 8.14 (1H, dt, J = 8.5, 1.0 Hz), 7.67 (1H, ddd, J = 8.5, 7.0, 1.0 Hz), 7.53 (1H, ddd, J = 8.5, 7.0, 1.0 Hz), 7.39 (1H, dt, J = 8.0, 1.5 Hz), 7.37 (1H, t, J = 1.5 Hz), 7.21 (1H, dt, J = 8.0, 1.5 Hz), 7.17 (1H, t, J = 8.0 Hz), 6.27 (1H, dd, J = 4.5, 2.0 Hz), 4.21 (1H, td, J = 7.0, 4.0 Hz), 4.14 (1H, dd, J = 18.0, 7.0 Hz), 4.10 (1H, dd, J = 18.0, 7.0 Hz), 2.84 (1H, sept-d, J = 7.0, 2.0 Hz), 1.22 (3H, d, J = 7.0 Hz), 1.10 (3H, d, J = 7.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 170.2, 169.8, 164.3, 146.3, 136.9, 132.4, 131.3, 131.0, 130.8, 130.0, 128.8, 126.6, 122.4, 120.4, 114.4, 99.2, 43.7, 36.1, 28.2, 19.0, 18.9; IR (liq. film): 2973, 1781, 1737, 1450, 1391, 1065, 998, 965, 733, 708 cm -1 ; HRMS (ESI-TF) Calcd for C 21 H Bra ([M+a] + ) , Found , f: IC, H/IPA = 3:1, flow rate = 0.5 ml/min, λ = 210 nm, 24.4 min (minor diastereomer), 30.1 min (major; major diastereomer), 33.5 min (minor; major diastereomer), 43.1 min (minor diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.29 (1H, d, J = 8.0 Hz), 8.18 (1H, d, J = 8.0 Hz), 8.12 (1H, dt, J = 8.0, 1.0 Hz), 7.85 (1H, dt, J = 8.0, 1.0 Hz), 7.77 (1H, d, J = 8.0 Hz), 7.61 (2H, t, J = 8.0 Hz), 7.51 (1H, t, J = 8.0 Hz), 7.50 (1H, t, J = 8.0 Hz), 7.47 (1H, d, J = 8.0 Hz), 7.41 (1H, t, J = 8.0 Hz), 6.38 (1H, dd, J = 4.5, 2.0 Hz), 5.22 (1H, brs), 4.23 (1H, dd, J = 17.5, 7.5 Hz), 4.13 (1H, dd, J = 17.5, 6.5 Hz), 2.84 (1H, sept-d, J = 7.0, 2.0 Hz), 1.20 (3H, d, J = 7.0 Hz), 1.08 (3H, d, J = 7.0 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 170.1, 169.7, 164.3, 146.2, 134.0, 132.2, 131.9, 131.0, 130.7, 129.1, 128.8, 126.8, 126.5, 126.3, 126.0, 124.8, 123.1, 120.3, 114.4, 100.3, 38.0, 36.3, 28.2, 19.0, one carbon was not found - S5 -

7 probably due to overlapping; IR (liq. film): 2973, 1781, 1738, 1450, 1391, 1055, 969, 910, 782, 733 cm -1 ; HRMS (ESI-TF) Calcd for C 25 H a ([M+a] + ) Found g: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 30.8 min (minor diastereomer), 33.2 min (major; major diastereomer), 38.5 min (minor; major diastereomer), 47.7 min (minor diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.27 (1H, dt, J = 8.0, 1.0 Hz), 8.15 (1H, dt, J = 8.0, 1.0 Hz), 7.68 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.54 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.31 (1H, dd, J = 2.0, 1.0 Hz), 6.29 (2H, dd, J = 4.0, 2.0 Hz), 6.23 (1H, d, J = 4.0 Hz), 4.34 (1H, td, J = 7.0, 4.0 Hz), 4.20 (1H, dd, J = 18.0, 7.0 Hz), 4.03 (1H, dd, J = 18.0, 7.0 Hz), 2.87 (1H, sept-d, J = 7.0, 2.0 Hz), 1.21 (3H, d, J = 7.0 Hz), 1.10 (3H, d, J = 7.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 169.9, 169.8, 164.5, 148.8, 146.3, 142.6, 131.1, 130.8, 126.6, 120.4, 114.5, 110.6, 109.5, 98.7, 38.5, 34.6, 28.2, 19.1, 18.9; IR (liq. film): 2973, 1782, 1738, 1451, 1393, 1167, 1063, 1000, 966, 736 cm -1 ; HRMS (ESI-TF) Calcd for C 19 H a ([M+a] + ) Found h: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 25.1 min (minor diastereomer), 28.3 min (minor; major diastereomer), 34.4 min (major; major diastereomer), 36.9 min (minor diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.30 (1H, dt, J = 8.0, 1.0 Hz), 8.14 (1H, dt, J = 8.0, 1.0 Hz), 7.69 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.54 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 6.03 (1H, dd, J = 5.0, 2.0 Hz), 3.66 (1H, dd, J = 17.0, 6.0 Hz), 3.50 (1H, dd, J = 17.0, 7.5 Hz), 3.00 (1H, sept-d, J = 6.5, 2.0 Hz), 2.93 (1H, quin-dd, J = 7.0, 6.0, 5.0 Hz), 1.28 (3H, d, J = 6.5 Hz), 1.26 (3H, d, J = 7.0 Hz), 1.12 (3H, d, J = 6.5 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 170.7, 169.5, 164.9, 146.3, 131.1, 130.8, 126.5, 120.4, 114.5, 101.4, 37.4, 33.7, 28.3, 19.4, 19.1, 14.0; IR (liq. film): 2973, 1781, 1739, 1485, 1451, 1392, 1059, 984, 937, 752 cm -1 ; HRMS (ESI-TF) Calcd for C 16 H a ([M+a] + ) Found i: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 14.4 min (minor diastereomer), min (minor; major diastereomer), 19.9 min (major; major diastereomer), 20.8 min (minor diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.29 (1H, d, J = 8.0 Hz), 8.14 (1H, d, J = 8.0 Hz), 7.68 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 7.53 (1H, ddd, J = 8.0, 7.0, 1.0 Hz), 6.09 (1H, dd, J = 5.0, 2.0 Hz), 3.50 (1H, dd, J = 17.5, 7.0 Hz), 3.46 (1H, dd, J = 17.5, 7.0 Hz), 2.95 (1H, sept-d, J = 7.0, 2.0 Hz), 2.86 (1H, quin-d, J = 7.0, 5.0 Hz), 1.60 (1H, ddd, J = 10.0, 7.0, 5.0 Hz), (3H, m), (4H, m), 1.24 (3H, d, J = 7.0 Hz), 1.19 (3H, d, J = 7.0 Hz), 0.88 (3H, t, J = 7.0 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 170.9, 169.2, 164.9, 146.3, 131.1, 130.7, 126.4, 120.4, 114.5, 100.6, 38.3, 34.8, 31.7, 29.1, 28.3, 26.6, 22.5, , , 14.1; IR (liq. film): 2931, 1781, 1737, 1450, 1389, 1168, 1057, 975, 771, 752 cm -1 ; HRMS (ESI-TF) Calcd for C 20 H a ([M+a] + ) Found Ph 4j: IC, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 21.0 min (minor diastereomer), 24.7 min (minor; major diastereomer), 29.6 min (minor diastereomer), 31.6 min (major; major diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.29 (1H, d, J = 8.0 Hz), 8.14 (1H, d, J = 8.0 Hz), 7.68 (1H, t, J = 8.0 Hz), 7.53 (1H, t, J = 8.0 Hz), 7.27 (2H, t, J = 7.0 Hz), 7.19 (2H, d, J = 7.0 Hz), 7.17 (1H, t, J = 7.0 Hz), 6.11 (1H, dd, J = 5.0, 2.0 Hz), 3.56 (1H, dd, J = 17.5, 7.0 Hz), 3.51 (1H, dd, J = 17.5, 6.0 Hz), 2.99 (1H, sept-d, J =7.0, 2.0 Hz), 2.89 (1H, brsex, J = 6.5 Hz), 2.84 (1H, ddd, J = 18.0, 14.0, 6.5 Hz), 2.80 (1H, ddd, J = 18.0, 14.0, 6.5 Hz), 1.97 (1H, ddt, J = 14.0, 9.5, 6.5 Hz), 1.81 (1H, ddt, J = 14.0, 9.5, 6.5 Hz), 1.24 (3H, d, J = 7.0 Hz), 1.18 (3H, d, J = 7.0 Hz); 13 C MR (175 MHz, CDCl 3 ) δ 170.7, 169.4, 164.8, 146.3, 140.9, 131.1, 130.7, 128.6, 128.4, 126.4, 126.3, 120.4, 114.5, 100.6, 38.1, 34.8, 33.3, 30.8, 28.3, , ; IR (liq. film): 2972, 2932, 1780, 1737, 1485, 1451, 1389, 1060, 974, 910, 733 cm -1 ; HRMS (ESI-TF) Calcd for C 23 H a ([M+a] + ) Found k: IA, H/EtH = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 21.5 min (minor diastereomer), 25.9 min (minor diastereomer), 29.8 min (major; major diastereomer), 33.5 min (minor; major diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 8.28 (1H, dt, J = 8.5, 1.0 Hz), 8.14 (1H, dt, J = 8.5, 1.0 Hz), 7.67 (1H, ddd, J = 8.5, 7.0, 1.0 Hz), 7.53 (1H, ddd, J = 8.5, 7.0, 1.0 Hz), 6.09 (1H, dd, J = 5.0, 2.0 Hz), 3.41 (1H, dd, J = 17.0, 5.0 Hz), 3.32 (1H, dd, J = 17.0, 7.5 Hz), 2.89 (1H, sept-d, J = 7.0, 2.0 Hz), 2.83 (1H, dq, J = 7.5, 5.0 Hz), (6H, m), (5H, m), 1.22 (3H, d, J = 7.0 Hz), 1.11 (3H, d, J = 7.0 Hz); 13 C MR (126 MHz, CDCl 3 ) δ 171.3, 169.0, 165.0, 146.4, 131.2, 130.7, 126.4, 120.4, 114.5, 100.1, 43.6, 38.8, 31.9, 30.9, 30.4, 28.3, 26.6, 26.5, 26.4, 19.1, 18.9; IR (liq. - S6 -

8 film): 2928, 2853, 1780, 1738, 1450, 1389, 1062, 964, 751, 733 cm -1 ; HRMS (ESI-TF) Calcd for C 21 H a ([M+a] + ) Found CH 3 H DBU DBU CH 2 Cl 2,0 C CH 3 H, 0 C H 4h 5 7 a 2 AcH/Ac 2 0 C-rt LiH 30% H 2 2 THF/H2 0 C H H 8 6 Derivatization of 4h to thylsuccinic Acid 6: thanolysis of 4h: To a solution of 4h (157.2 mg, 0.5 mmol, 96% ee) in dichloromethane (5 ml) was added methanol (40.5 μl, 1.0 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (74.8 μl, 0.5 mmol) dropwise at 0 C. The reaction mixture was stirred for 5 min and diluted with 1 HCl aqueous solution to quench the reaction. The resulting aqueous phase was extracted with EA three times. The combined organic extracts were dried over a 2 S 4 and filtered. After concentration, the residue was purified by column chromatography on silica gel (H/EA = 5:1 as eluent) to give 5 in 98% yield and its diastereomeric ratio was >20:1. The enantiomeric purity of 5 was determined to be 96% ee by chiral stationary phase HPLC analysis. 5: IC, H/EtH = 20:1, flow rate = 0.5 ml/min, λ = 210 nm, 24.5 min (minor diastereomer), 28.4 min (major; major diastereomer), 29.4 min (minor diastereomer), 30.9 min (minor; major diastereomer); 1 H MR (500 MHz, CDCl 3 ) δ 5.85 (1H, dd, J = 5.0, 2.0 Hz), 3.70 (3H, s), 2.99 (1H, sept-d, J = 7.0, 2.0 Hz), (1H, m), 2.52 (1H, dd, J = 15.5, 6.0 Hz), 2.30 (1H, dd, J = 15.5, 7.5 Hz), 1.29 (3H, d, J = 7.0 Hz), 1.28 (3H, d, J = 7.0 Hz), 0.98 (3H, d, J = 7.0 Hz). Isomerization and thanolysis of 5: A solution of 5 (111.4 mg, 0.49 mmol) and DBU (73.3 μl, 0.49 mmol) in methanol (10 ml) was stirred at 0 C for 30 min. 1 HCl aqueous solution was then added to the mixture to quench the reaction. The mixture was extracted with EA three times and organic phases were washed with brine. The combined organic extracts were dried over a 2 S 4 and filtered. After evaporation, the residue was purified by column chromatography on silica gel (H/EA = 2:1 as eluent) to furnish 7 as a mixture of diastereomers in 87% yield. 7: 1 H MR (500 MHz, CDCl 3 ) δ 6.25 (0.5H, d, J = 8.5 Hz), 6.18 (0.5H, d, J = 8.5 Hz), 4.57 (0.5H, dd, J = 8.5, 5.0 Hz), 4.54 (0.5H, dd, J = 8.5, 5.0 Hz), (1.5H, s), (1.5H, s), 3.68 (1.5H, s), 3.67 (1.5H, s), (2H, m), (1H, m), (0.5H, sept-d, J = 7.0, 5.0 Hz), (0.5H, sept-d, J = 7.0, 5.0 Hz), 1.23 (1.5H, d, J = 7.0 Hz), 1.20 (1.5H, d, J = 7.0 Hz), 0.94 (1.5H, d, J = 7.0 Hz), 0.93 (1.5H, d, J = 7.0 Hz), 0.91 (3H, d, J = 7.0 Hz). -itrosation of 7 (S9): To a solution of 7 (77.8 mg, 0.3 mmol) in glacial acetic acid (1 ml) and acetic anhydride (2 ml) was added a 2 (207.0 mg, 3.0 mmol) at 0 C. The reaction mixture was allowed to warm to room temperature and stirred for 18 hours. The resulting solution was poured onto ice and the aqueous phase was extracted with diethyl ether twice. The organic phase was washed with water, saturated ahc 3 aqueous solution, and brine. The combined organic extracts were dried over a 2 S 4, filtered, and concentrated. Purification of the residue by column chromatography on silica gel (H/EA = 10:1 as eluent) afforded 8 as a mixture of diastereomers in 77 % yield. 8: 1 H MR (500 MHz, CDCl 3 ) δ 4.94 (0.5H, d, J = 9.0 Hz), 4.86 (0.5H, d, J = 9.0 Hz), (1H, m), (1.5H, s), (1.5H, s), 3.62 (1.5H, s), 3.61 (1.5H, s), 3.08 (1H, dd, J = 17.0, 10.0 Hz), 2.57 (1H, dd, J = 17.5, 5.0 Hz), 2.49 (1H, d-sept, J = 9.0, 7.0 Hz), 1.35 (1.5H, d, J = 7.0 Hz), 1.33 (1.5H, d, J = 7.0 Hz), 1.11 (3H, d, J = 7.0 Hz), 0.61 (1.5H, d, J = 7.0 Hz), 0.59 (1.5H, d, J = 7.0 Hz). Hydrolysis of 8 (S9): A solution of 8 (66.3 mg, 0.23 mmol) in THF (23 ml) was treated with 30% H 2 2 solution (1.3 ml) and a 1.0 M aqueous solution of LiH (2.3 ml, 2.3 mmol) at 0 C for 4 hours. Then, a saturated aqueous solution of ahs 3 was added to the resulting solution until peroxides were completely reduced. After concentration, the residual - S7 -

9 aqueous phase was washed with diethyl ether, acidified with conc. HCl and extracted with EA twice. The organic extracts were dried over a 2 S 4 and evaporated under reduced pressure to give (S)-6 in 75 % yield. (S)-6: 1 H MR (500 MHz, CD 3 D) δ 2.83 (1H, dqd, J = 8.0, 7.0, 6.0), 2.66 (1H, dd, J = 17.0, 8.0 Hz), 2.39 (2H, dd, J = 17.0, 6.0 Hz), 1.21 (3H, d, J = 7.0 Hz); [α] 27 D (c = 1.18, EtH) [lit. (S10) [α] 24.2 D (c = 1.89, EtH) for S isomer, 99% ee]. Conservation of Enantiomeric Purity: The enantiomeric purity of 6 was determined by HPLC analysis after esterification. Esterification of 6: To a solution of 6 (21.0 mg, 0.16 mmol), tetrabutylammonium iodide (TBAI) (5.9 mg, 0.01 mmol) and K 2 C 3 (132.7 mg, 0.96 mmol) in,-dimethylformamide (DMF) (2 ml) was added benzyl bromide (57.1 μl, 0.48 mmol) dropwise at room temperature. The reaction mixture was vigorously stirred for 8 hours and diluted with H 2. The resulting aqueous solution was extracted with diethyl ether three times. The combined organic extracts were dried over a 2 S 4 and filtered. Evaporation of solvents and purification of the residue by column chromatography on silica gel (H/EA = 10:1 as eluent) gave 9 in 83% yield. The enantiomeric purity of 9 was determined to be 95% ee by chiral stationary phase HPLC analysis. 9: DH, H/IPA = 10:1, flow rate = 0.5 ml/min, λ = 210 nm, 16.1 min (R), 21.1 min (S); 1 H MR (700 MHz, CDCl 3 ) δ (4H, m), (6H, m), 5.12 (1H, d, J = 12.6 Hz), 5.10 (1H, d, J = 11.9 Hz), 5.08 (1H, d, J = 12.6 Hz), 5.07 (1H, d, J = 11.9 Hz), 3.00 (1H, sex, J = 7.0 Hz), 2.81 (1H, dd, J = 16.1, 7.0 Hz), 2.48 (1H, dd, J = 16.1, 7.0 Hz), 1.24 (3H, d, J = 7.0 Hz). - S8 -

10 Additional Experimental Data and Discussion: Effect of Phenol Structure on the Selectivity: α,β-unsaturated -acylbenzotriazole 3a (24.9 mg, 0.10 mmol) and 1a (Ar) 3 H 2 (0.02 equiv, 2.0 μmol) were placed in a dried test tube and dissolved into toluene (1.0 ml) under Ar atmosphere. Azlactone 2 (14.0 mg, 0.11 mmol) was then introduced dropwise slowly at 40 C and the stirring was continued for indicated hours. A solution of trifluoroacetic acid in toluene (0.5 M, 20 μl) was added to the mixture at 40 C to quench the reaction. The resulting mixture was poured into ice-cooled 1 HCl aqueous solution and the aqueous phase was extracted with EA. The combined organic phase was washed with brine, dried over a 2 S 4, and filtered. After removing all volatiles by evaporation, purification of the residue by column chromatography on silica gel (H/EA = 5:1 as eluent) afforded 4a, whose enantiomeric excess was determined by HPLC analysis. The results with a series of catalysts that possess different phenols are listed in Table S1. Although it seems to be difficult to see any tendency of correlation between the phenol structure and enantioselectivity, the use of 3,5-Cl 2 C 6 H 3 H leads to the highest selectivity so far. Table S1. ptimization of Phenol Structure entry catalyst time (h) yield (%) ee (%) 1 1a (Ph) 3 H a (4-CF 3 C 6 H 4 ) 3 H a (4-F C 6 H 4 ) 3 H a (4-Cl C 6 H 4 ) 3 H a (4-Br C 6 H 4 ) 3 H a (4- C 6 H 4 ) 3 H a (4- C 6 H 4 ) 3 H a (2-naphthoxide) 3 H a (2-Cl C 6 H 4 ) 3 H a (2- C 6 H 4 ) 3 H a (2-Ph C 6 H 4 ) 3 H a (3-Cl C 6 H 4 ) 3 H a (3,5-Cl 2 C 6 H 3 ) 3 H a (3,5-2 C 6 H 3 ) 3 H a (2,4-2 C 6 H 3 ) 3 H a (2,6-2 C 6 H 3 ) 3 H b (Ph) 3 H b (4-Cl C 6 H 4 ) 3 H S9 -

11 Selectivity Dependence on Phenol Concentration: To a solution of 1a Cl (8.24 mg, μmol) in toluene (2.4 ml) was introduced a 1.0 M THF solution of K t Bu (12.5 μl, 12.5 μmol) at 78 ºC and the mixture was stirred there for 30 min. After addition of a solution of phenol (PhH or 4-Cl C 6 H 4 H) in 0.1 ml of toluene at 40 ºC, the resulting catalyst solution was aged for 30 min. Then, -acylbenzotriazole 3a (62.3 mg, 0.25 mmol) and azlactone 2 (35.0 mg, mmol) were added sequentially, and stirring was continued at 40 ºC. The reaction was quenched by the addition of a solution of trifluoroacetic acid (0.5 M, 150 μl) at 40 ºC and the whole mixture was poured into ice-cooled 1 HCl aqueous solution. After extractive workup with EA and evaporation of solvents, the crude residue was purified by silica gel column chromatography (H/EA = 5:1 as eluent) to give the adduct 4a, whose enantiomeric excess was determined by HPLC analysis. The enantioselectivity of the reaction was plotted against the concentration of phenol under the influence of 1a as a cationic component of the catalyst (Fig. S1). The form of each plotting clearly showed the strong dependence of the selectivity on the phenol concentration. In consideration of this observation and the effect of the catalyst concentration described in the manuscript, there would be an equilibrium in the assembly of an enolate ion pair such as shown in Fig. S2. The lower enantioselectivity observed under lower phenol concentration might stem from the intervention of the enolate assembly of either A or B. Higher concentration of phenol should push this equilibrium to right and increased population of the assembly C would lead to the higher selectivity [30 mol% of phenol (30 mm of phenol concentration) corresponds to that of the optimized reaction conditions, which is 0.2 mmol scale with 1 mol% of 1a (Ph) 3 H 2 in 0.2 ml of toluene]. % ee of 4a a' 1a + PhH 1a' 1a + 4-Cl-C6H4H 4-Cl C 6 H phenol mol% Fig. S1. Selectivity Dependence on Phenol Concentration Fig. S2. - S10 -

12 Crystallographic Structure Determination: Recrystallization of 1a (Ph) 3 H 2 (CCDC ): Tetraaminophosphonium phenoxide 1a (Ph) 3 H 2 was recrystallized from hexane/diethyl ether solvent system at room temperature. The single crystal thus obtained was mounted on CryoLoop. Data of X-ray diffraction were collected at 153 K on a Brucker SMART APEX CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = Å). An absorption correction was made using SADABS. The structure was solved by direct methods and Fourier syntheses, and refined by full-matrix least squares on F 2 by using SHELXTL (S11). All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms bonded to nitrogen and oxygen atoms were located from a difference synthesis and their coordinates and isotropic thermal parameters refined. The other hydrogen atoms were placed in calculated positions. The crystallographic data were summarized in Table S2, S3 and RTEP diagram was shown in Fig. S3. Table S2. Crystal Data and Structure Refinement for 1a (Ph) 3 H 2. Empirical formula C54 H P Formula weight Temperature 153(2) K Wavelength Å Crystal system rthorhombic Space group P2(1)2(1)2(1) Unit cell dimensions a = (5) Å α= 90. b = (10) Å β= 90. c = (11) Å γ = 90. Volume (4) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1808 Crystal size 0.60 x 0.20 x 0.10 mm 3 Theta range for data collection 1.37 to Index ranges -11<=h<=14, -28<=k<=22, -27<=l<=28 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 581 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.13(8) Largest diff. peak and hole and e.å -3 Table S3. Hydrogen Bonds for 1a (Ph) 3 H 2 [Å and ]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) (1)-H(58)...(3)#1 0.95(4) 1.60(4) 2.539(3) 168(4) (2)-H(57)...(3)#2 0.94(4) 1.58(4) 2.506(3) 167(3) (4)-H(56)...(1)#3 0.89(3) 2.00(3) 2.881(3) 172(2) (2)-H(55)...(2)#4 0.89(3) 1.97(3) 2.838(3) 163(2) Symmetry transformations used to generate equivalent atoms: #1 x,y-1,z; #2 x,y-1,z+1; #3 x-1,y,z; #4 x-1,y,z-1. - S11 -

13 Fig. S3. Molecular Structure of Tetraaminophosphonium Phenoxide 1a (Ph) 3 H 2. All calculated hydrogen atoms are omitted for clarity. Purple = phosphorus, blue = nitrogen, red = oxygen, black = carbon. References: S1. D. Uraguchi, S. Sakaki, T. oi, J. Am. Chem. Soc. 129, (2007). S2. D. Uraguchi, S. Sakaki, Y. Ueki, T. Ito, T. oi, Heterocycles 76, 1081 (2008). S3. D. Uraguchi, Y. Ueki, T. oi, J. Am. Chem. Soc. 130, (2008). S4. A. Barco, S. Benetti, C. De Risi, G. P. Pollini, G. Spalluto, V. Zanirato, Tetrahedron 52, 4719 (1996). S5. A. R. Katritzky, Y. Zhang, S. K. Singh, Synthesis 2795 (2003). S6. T. Tozawa, H. agao, Y. Yamane, T. Mukaiyama, Chem. Asian J. 2, 123 (2007). S7. C. Pardin, J.. Pelletier, W. D. Lubell, J. W. Keillor, J. rg. Chem. 73, 5766 (2008). S8. A. R. Katritzky, M. Wang, S. Zhang, ARKIVC 9, 19 (2001). S9. D. A. Evans, P. H. Carter, C. J. Dinsmore, J. C. Barrow, J. L. Katz, D. W. Kung, Tetrahedron Lett. 38, 4535 (1997). S10. E. J. Eisenbraun, S. M. McElvain, J. Am. Chem.Soc. 77, 3383 (1955). S11. G. M. Sheldrick, SHELXTL 5.1, Bruker AXS Inc., Madison, Wisconsin, S12 -